Semiclassical Path Integral Calculation of Nonlinear Optical Spectroscopy

• DOI: 10.1021/acs.jctc.7b01063
• Publication Date: 2017-12-15T18:27:11Z
• Authors: Justin Provazza; Francesco Segatta; Marco Garavelli; David F. Coker
• Keywords: Semiclassical physics

Computation of nonlinear optical response functions allows for an in-depth connection between theory and experiment. Experimentally recorded spectra provide a high density information, but to objectively disentangle overlapping signals reach detailed reliable understanding the system dynamics, measurements must be integrated with theoretical approaches. Here, we present new, highly accurate efficient trajectory-based semiclassical path integral method computing higher order non-Markovian open quantum systems. The approach is, in principle, applicable general Hamiltonians does not require any restrictions on form intrasystem or system-bath couplings. This is systematically improvable shown valid parameter regimes where perturbation theory-based methods qualitatively breakdown. As test methodology presented here, study model coupled dimer which compare against numerically exact results standard approximate calculations. Additionally, monomer discrete vibronic states that serves as starting point future investigation signatures electronic spectroscopy.